Fuel additive

ABSTRACT

A diesel fuel additive for use in association with bio-diesel fuel and/or petroleum derived diesel fuel having one or more pour-point depressant(s), wherein the pour-point depressant(s) polyglycerol polyricinoleate. Augmentive agents may include at least one of ethylene vinyl acetate and polyethylene vinyl acetate and at least one polyglycerol ester of mixed fatty acids.

CROSS-REFERENCE TO RELATED APPLICATION(S)

This application is a continuation of U.S. patent application Ser. No.12/131,191, filed Jun. 2, 2008, the entirety of which is herebyincorporated by reference, which claims the benefit of U.S. ProvisionalPatent Application No. 60/940,986, filed May 31, 2007, the entirety ofwhich is hereby incorporated by reference.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention relates in general to fuel additives and, moreparticularly, to diesel fuel additives which improve low temperaturehandling properties of diesel fuels—including bio-diesel fuels and/orpetroleum derived diesel fuels.

2. Background Art

Vehicles having engines which consume diesel fuel have been known in theart for years, and are becoming increasingly popular in industrializednations where, among other things, the cost of gasoline has becomeprohibitively expensive. As the popularity of vehicles with dieselengines has grown, so too has the demand for a plurality of differenttypes of diesel fuels, including both bio-diesel fuels and petroleumderived diesel fuels. While the utilization of vehicles with dieselengines has become increasingly popular, issues relative low temperaturehandling properties remains largely problematic, especially with regardto bio-diesel fuels. In particular, pure bio-diesel (e.g. 100% methylsoyate) typically stops flowing freely at approximately 29 degreesFahrenheit. Indeed, vehicles with diesel engines consuming bio-dieselfuels can be, during normal operation, exposed to extreme temperaturesranging from approximately less than 0 degrees Fahrenheit toapproximately more than 100 degrees Fahrenheit.

Accordingly, it is an object of the present invention to provide dieselfuels, especially bio-diesel fuels, having additives which enableassociated vehicles to freely start and/or operate during normaluse—including exposure to extreme temperatures, such as, for example,during winter in the United States, Canada, Europe, etcetera.

These and other objects of the present invention will become apparent inlight of the present specification, claims, and/or drawings.

SUMMARY OF THE INVENTION

In one embodiment, the present invention is directed to a diesel fueladditive comprising at least one solvent, and at least one pour-pointdepressant, wherein the at least one pour-point depressant comprises apolyglycerol ester.

Preferably the majority species of the above-identified polyglycerolesters comprise polyglycerol polyol chains that have been esterifiedwith alkyl-carboxyl moieties or fatty acids. It will be understood thatthe above-identified polyglycerols may comprise several species withvarious structures such as, but not limited to linear, branched, and/orcyclic polyglycerol polyols, which may be non-esterified, partiallyesterified, and/or completely esterified and be ester and/or hydroxylterminated.

In a preferred embodiment of the present invention, the at least onepour-point depressant is represented by the following chemicalstructure:

wherein n is an integer ranging from approximately 1 to approximately100, more preferably from approximately 1 to approximately 25, and mostpreferably from approximately 1 to approximately 5; wherein R₁-R₁₂ arethe same or different and comprise: (1) H; (2) a straight and/orbranched alkyl, cycloalkyl, polycycloalkyl, heterocycloalkyl, aryl,alkaryl, aralkyl, alkoxy, alkenyl, and/or alkynyl group containingapproximately 1 to approximately 100 carbon atom(s), more preferablyapproximately 1 to approximately 25 carbon atom(s); (3) a silyl and/orsiloxyl group containing approximately 1 to approximately 100 siliconatom(s), more preferably approximately 1 to approximately 25 siliconatom(s); and/or (4) mixtures thereof; and wherein the carbon or siliconatom(s) may be a linking group to, or part of, one or more functionalgroups selected from the group consisting of alcohols, thiols,thioethers, nitriles, nitro constituents, sulfoxides, sulfonates,phosphonium constituents, phosphonates, phosphonites, ammoniumconstituents, carbonyls, carbonates, carbamates, ketones, esters,amides, ethers, amines, and mixtures thereof.

In another preferred embodiment of the present invention, the at leastone pour-point depressant is represented by the following chemicalstructure:

wherein n is an integer ranging from approximately 1 to approximately100, more preferably from approximately 1 to approximately 25, and mostpreferably from approximately 1 to approximately 5; and wherein R₁-R₁₂are the same or different and are selected from the group comprising:(1) H; (2) a straight and/or branched alkyl, cycloalkyl, polycycloalkyl,heterocycloalkyl, aryl, alkaryl, aralkyl, alkoxy, alkenyl, and/oralkynyl group containing approximately 1 to approximately 100 carbonatom(s), more preferably approximately 1 to approximately 25 carbonatom(s); and/or (3) mixtures thereof.

In yet another preferred embodiment of the present invention, the atleast one pour-point depressant comprises polyglycerol esters of mixedfatty acids.

In a preferred embodiment of the present invention, the at least onepour-point depressant is represented by the following chemicalstructure:

wherein n is an integer ranging from approximately 1 to approximately100, more preferably from approximately 1 to approximately 15, and mostpreferably from approximately 1 to approximately 5; wherein x₁-x₆ arethe same or different and comprise an integer ranging from approximately1 to approximately 100, more preferably from approximately 1 toapproximately 20, and most preferably from approximately 1 toapproximately 15; wherein y₁-y₃ are the same or different and comprisean integer ranging from approximately 1 to approximately 50, morepreferably from approximately 1 to approximately 10, and most preferablyfrom approximately 1 to approximately 5; wherein R₁-R₁₂ are the same ordifferent and are selected from the group comprising: (1) H; (2) astraight and/or branched alkyl, cycloalkyl, polycycloalkyl,heterocycloalkyl, aryl, alkaryl, aralkyl, alkoxy, alkenyl, and/oralkynyl group containing approximately 1 to approximately 100 carbonatom(s), more preferably approximately 1 to approximately 25 carbonatom(s); (3) a silyl and/or siloxyl group containing approximately 1 toapproximately 100 silicon atom(s), more preferably approximately 1 toapproximately 25 silicon atom(s); and/or (4) mixtures thereof; andwherein the carbon or silicon atom(s) may be a linking group to, or partof, one or more functional groups selected from the group consisting ofalcohols, thiols, thioethers, nitriles, nitro constituents, sulfoxides,sulfonates, phosphonium constituents, phosphonates, phosphonites,ammonium constituents, carbonyls, carbonates, carbamates, ketones,esters, amides, ethers, amines, and mixtures thereof.

In yet another preferred embodiment of the present invention, the atleast one pour-point depressant is represented by the following chemicalstructure:

wherein n is an integer ranging from approximately 1 to approximately100, more preferably from approximately 1 to approximately 15, and mostpreferably from approximately 1 to approximately 5; wherein x₁-x₆ arethe same or different and comprise an integer ranging from approximately1 to approximately 100, more preferably from approximately 1 toapproximately 20, and most preferably from approximately 1 toapproximately 15; wherein y₁-y₃ are the same or different and comprisean integer ranging from approximately 1 to approximately 50, morepreferably from approximately 1 to approximately 10, and most preferablyfrom approximately 1 to approximately 5; and wherein R₁-R₁₂ are the sameor different and comprise: (1) H; (2) a straight and/or branched alkyl,cycloalkyl, polycycloalkyl, heterocycloalkyl, aryl, alkaryl, aralkyl,alkoxy, alkenyl, and/or alkynyl group containing approximately 1 toapproximately 100 carbon atom(s), more preferably approximately 1 toapproximately 25 carbon atom(s); and/or (3) mixtures thereof.

In yet another preferred embodiment of the present invention, the atleast one pour-point depressant comprises polyglycerol polyricinoleate.

In another embodiment, the present invention is directed to a dieselfuel additive comprising at least one solvent, a first pour-pointdepressant, and a second pour-point depressant, wherein at least one ofthe first and second pour-point depressants comprises a polyglycerolester. In this embodiment the first pour-point depressant preferablycomprises polyglycerol polyricinoleate, and the second pour-pointdepressant preferably comprises polyglycerol esters of mixed fattyacids.

In another aspect of the present invention, the at least one solventcomprises hydrocarbons, aromatic hydrocarbons, alcohols, ethers,nitriles, mineral spirits, bio-diesel fuel, petroleum derived dieselfuel, and/or mixtures thereof.

In yet another aspect of the present invention, a bio-diesel fuel and/orpetroleum derived diesel fuel is associated with a diesel fuel additiveas disclosed supra.

In one embodiment, the present invention is directed to a method forusing a diesel fuel additive comprising the steps of: providing asolvent; providing a diesel fuel additive comprising at least onepour-point depressant, wherein the at least one pour-point depressantcomprises polyglycerol polyricinoleate and/or polyglycerol esters ofmixed fatty acids; and associating the diesel fuel additive with thesolvent.

In another aspect of the present invention, ethylene vinyl acetate (EVA)and/or polyethylene vinyl acetate (PEVA) may be utilized as a pour-pointdepressant, for example, in cooperation with one or more pour-pointdepressant(s), such as a polyglycerol ester as disclosed herein.

DETAILED DESCRIPTION OF THE INVENTION

While this invention is susceptible of embodiment in many differentforms, there is shown in the drawings and will herein be described indetail several specific embodiments with the understanding that thepresent disclosure is to be considered as an exemplification of theprinciples of the invention and is not intended to limit the inventionto the embodiments illustrated.

In accordance with the present invention a diesel fuel additive isprovided which comprises one or more solvent(s), and one or morepour-point depressant(s), such as polyglycerol esters, ethylene vinylacetate and/or polyethylene vinyl acetate. As is shown experimentallyherein below, one or more pour-point depressant(s) substantiallyimproves the low temperature handling properties of dieselfuels—especially bio-diesel fuels.

Preferably the majority species of the above-identified polyglycerolesters comprise polyglycerol polyol chains that have been esterifiedwith alkyl-carboxyl moieties or fatty acids. It will be understood thatthe above-identified polyglycerols may comprise several species withvarious structures such as, but not limited to linear, branched, and/orcyclic polyglycerol polyols, which may be non-esterified, partiallyesterified, and/or completely esterified and be ester and/or hydroxylterminated.

In one embodiment of the present invention, the polyglycerol esterpour-point depressant is represented by the following chemicalstructure:

wherein n is an integer ranging from approximately 1 to approximately100, more preferably from approximately 1 to approximately 25, and mostpreferably from approximately 1 to approximately 5; wherein R₁-R₁₂ arethe same or different and comprise: (1) H; (2) a straight and/orbranched alkyl, cycloalkyl, polycycloalkyl, heterocycloalkyl, aryl,alkaryl, aralkyl, alkoxy, alkenyl, and/or alkynyl group containingapproximately 1 to approximately 100 carbon atom(s), more preferablyapproximately 1 to approximately 25 carbon atom(s); (3) a silyl and/orsiloxyl group containing approximately 1 to approximately 100 siliconatom(s), more preferably approximately 1 to approximately 25 siliconatom(s); and/or (4) mixtures thereof; and wherein the carbon or siliconatom(s) may be a linking group to, or part of, one or more functionalgroups selected from the group consisting of alcohols, thiols,thioethers, nitriles, nitro constituents, sulfoxides, sulfonates,phosphonium constituents, phosphonates, phosphonites, ammoniumconstituents, carbonyls, carbonates, carbamates, ketones, esters,amides, ethers, amines, and mixtures thereof.In this embodiment, the pour-point depressant is preferably representedby the following chemical structure:

wherein n is an integer ranging from approximately 1 to approximately100, more preferably from approximately 1 to approximately 25, and mostpreferably from approximately 1 to approximately 5; and wherein R₁-R₁₂are the same or different and are selected from the group comprising:(1) H; (2) a straight and/or branched alkyl, cycloalkyl, polycycloalkyl,heterocycloalkyl, aryl, alkaryl, aralkyl, alkoxy, alkenyl, and/oralkynyl group containing approximately 1 to approximately 100 carbonatom(s), more preferably approximately 1 to approximately 25 carbonatom(s); and/or (3) mixtures thereof. For example, the pour-pointdepressant disclosed supra may include polyglycerol esters of mixedfatty acids, such as Drewpol 3-5-M, which is commercially available fromStepan Company of Northfield, Ill. It will be understood that while one,preferred polyglycerol ester has been disclosed for illustrativepurposes only, any one of a number of other polyglycerol esters thatwould be known to those having ordinary skill in the art having thepresent disclosure before them are likewise contemplated for use inaccordance with the present invention.

In another embodiment of the present invention, the polyglycerol esterpour-point depressant is represented by the following chemicalstructure:

wherein n is an integer ranging from approximately 1 to approximately100, more preferably from approximately 1 to approximately 15, and mostpreferably from approximately 1 to approximately 5; wherein x₁-x₆ arethe same or different and comprise an integer ranging from approximately1 to approximately 100, more preferably from approximately 1 toapproximately 20, and most preferably from approximately 1 toapproximately 15; wherein y₁-y₃ are the same or different and comprisean integer ranging from approximately 1 to approximately 50, morepreferably from approximately 1 to approximately 10, and most preferablyfrom approximately 1 to approximately 5; wherein R₁-R₁₂ are the same ordifferent and are selected from the group comprising: (1) H; (2) astraight and/or branched alkyl, cycloalkyl, polycycloalkyl,heterocycloalkyl, aryl, alkaryl, aralkyl, alkoxy, alkenyl, and/oralkynyl group containing approximately 1 to approximately 100 carbonatom(s), more preferably approximately 1 to approximately 25 carbonatom(s); (3) a silyl and/or siloxyl group containing approximately 1 toapproximately 100 silicon atom(s), more preferably approximately 1 toapproximately 25 silicon atom(s); and/or (4) mixtures thereof; andwherein the carbon or silicon atom(s) may be a linking group to, or partof, one or more functional groups selected from the group consisting ofalcohols, thiols, thioethers, nitriles, nitro constituents, sulfoxides,sulfonates, phosphonium constituents, phosphonates, phosphonites,ammonium constituents, carbonyls, carbonates, carbamates, ketones,esters, amides, ethers, amines, and mixtures thereof.

In this embodiment, the pour-point depressant is preferably representedby the following chemical structure:

wherein n is an integer ranging from approximately 1 to approximately100, more preferably from approximately 1 to approximately 15, and mostpreferably from approximately 1 to approximately 5; wherein x₁-x₆ arethe same or different and comprise an integer ranging from approximately1 to approximately 100, more preferably from approximately 1 toapproximately 20, and most preferably from approximately 1 toapproximately 15; wherein y₁-y₃ are the same or different and comprisean integer ranging from approximately 1 to approximately 50, morepreferably from approximately 1 to approximately 10, and most preferablyfrom approximately 1 to approximately 5; and wherein R₁-R₁₂ are the sameor different and comprise: (1) H; (2) a straight and/or branched alkyl,cycloalkyl, polycycloalkyl, heterocycloalkyl, aryl, alkaryl, aralkyl,alkoxy, alkenyl, and/or alkynyl group containing approximately 1 toapproximately 100 carbon atom(s), more preferably approximately 1 toapproximately 25 carbon atom(s); and/or (3) mixtures thereof. Forexample, the pour-point depressant disclosed supra may includepolyglycerol polyricinoleate, such as Drewpol PGPR, which iscommercially available from Stepan Company of Northfield, Ill. Onceagain, it will be understood that while a, preferred polyglycerol esterhas been disclosed for illustrative purposes only, any one of a numberof other polyglycerol esters that would be known to those havingordinary skill in the art having the present disclosure before them arelikewise contemplated for use in accordance with the present invention.

As is shown experimentally herein below, ethylene vinyl acetate (EVA)and/or polyethylene vinyl acetate (PEVA) may be utilized as a pour-pointdepressant (i.e. augmentive agent), for example, in cooperation with oneor more pour-point depressant(s), such as a polyglycerol ester asdisclosed herein. Surprisingly, utilization of the augmentive agent incooperation with one or more pour-point depressant(s) appears tosynergistically lower the pour-point of an associated fuel—even at lowconcentrations. It will be understood that EVA and PEVA are commerciallyavailable from any one of a number of common vendors including, amongothers, MidContinental Chemical Company and/or Aldrich Chemicals.

Preferred solvents for use in accordance with the present inventioninclude, for example, hydrocarbons (e.g. 2-ethylhexyl isononanoate),aromatic hydrocarbons (e.g. benzene, toluene, xylene(s)), alcohols (e.g.isopropanol), ethers, nitriles, mineral spirits, bio-diesel fuel,petroleum derived diesel fuel, and/or mixtures thereof. While theabove-identified solvents have been disclosed for use in accordance withthe present invention, any one of a number of other solvents arelikewise contemplated for use.

In another aspect of the present invention a diesel fuel additive isdisclosed which comprises one or more solvent(s), a first pour-pointdepressant, and a second pour-point depressant, wherein the first and/orsecond pour-point depressant comprises a polyglycerol ester. In thisembodiment the first pour-point depressant preferably comprisespolyglycerol polyricinoleate, and the second pour-point depressantpreferably comprises a polyglycerol ester of mixed fatty acids.

It will be understood that the fuel additives disclosed herein can beassociated with bio-diesel fuel and/or petroleum derived diesel fuel.Regardless of its ordinary meaning, the term bio-diesel herein refers toa diesel-equivalent, processed fuel derived from biological sources(e.g. vegetable oils), which can be used in unmodified and/or modifieddiesel engine vehicles.

The present invention is further directed to a method for using a dieselfuel additive comprising the steps of: (1) providing a solvent; (2)providing a diesel fuel additive comprising at least one pour-pointdepressant, wherein the at least one pour-point depressant comprisespolyglycerol polyricinoleate and/or polyglycerol esters of mixed fattyacids; and (3) associating the diesel fuel additive with the solvent.Once the diesel fuel additive has been associated with the solvent, thesame can be consumed by a vehicle having a diesel engine. One benefit,among others, of using such a diesel fuel additive is that the dieselfuel can be poured and/or consumed at substantially lower temperaturesthan without the additive.

In support of the present invention, several experiments were conductedto determine the pour-point of different diesel fuels having one or moreadditives relative to the same without such additives.

Experiment No. 1

In this experiment a bio-diesel fuel additive was prepared by combiningthe following chemicals:

Chemical Concentration (Weight %) Xylene—solvent (Aldrich) 30Isopropanol—solvent (Aldrich) 20 Coldflow 105—pour-point depressant 20(MidContinental Chemical Company) Drewpol PGPR (Stepan)—pour-pointdepressant 10 Drewpol 3-5-M (Stepan)—pour-point depressant 20

After preparing the additive, the pour-point of several diesel fuelshaving the above-identified additive was compared to the pour-point ofthe same fuels without the additive. The results are tabulated hereinbelow:

Diesel Fuel Pour-Point (F) Iowa B-20 (no additive) −3 Iowa B-20 (0.1%additive, 1 pint/saddle tank) −18 Illinois B-11 (no additive) −3Illinois B-11 (0.2% additive, 1 quart/saddle tank) −29 B-100 (noadditive) 29 B-100 (0.5% additive, 2 quarts/saddle tank) <−34

Experiment No. 2

In this experiment a plurality of bio-diesel fuel additive formulationswere prepared. After preparing the formulations, the pour-point of eachformulation was measured and is provided herein below:

Diesel Fuel/Additive Formulation Concentration (Weight %) Pour-Point (F)B-100 (no additive) 100 28 B-100* 99.78 19 60% EVA 0.22 B-100* 99.57 1760% EVA 0.43 B-100* 99.37 18 60% EVA 0.43 Drewpol PGPR 0.19 B-100* 99.671 60% EVA 0.22 Drewpol 3-5-M 0.11 B-100* 99.53 <−22 60% EVA 0.22 Drewpol3-5-M 0.11 Drewpol PGPR 0.14 B-100* 98.88 19 Drewpol 3-5-M 1.12 B-100*98.03 13 Drewpol 3-5-M 1.12 Drewpol PGPR 0.85 B-100* 99.58 29 DrewpolPGPR 0.42 B-100* 98.95 16 Drewpol 3-5-M 0.42 Drewpol PGPR 0.63 *It willbe understood that in the formulations provided in Experiment No. 2,nominal amounts of non-native solvents have been uniformly omitted fromthe formulation description for comparative purposes.

The foregoing description merely explains and illustrates the inventionand the invention is not limited thereto except insofar as the appendedclaims are so limited, as those skilled in the art who have thedisclosure before them will be able to make modifications withoutdeparting from the scope of the invention.

What is claimed is:
 1. A fuel additive comprising polyglycerol polyricinoleate.
 2. The fuel additive according to claim 1, wherein the fuel additive comprises a diesel fuel additive.
 3. The fuel additive according to claim 1, wherein polyglycerol polyricinoleate is present in an amount of about 0.14% wt when the fuel additive is added to fuel present in an amount of about 99.53% wt.
 4. The fuel additive according to claim 1, wherein polyglycerol polyricinoleate is present in an amount of about 0.14% wt when the fuel additive is added to diesel fuel present in an amount of about 99.53% wt.
 5. The fuel additive according to claim 1, wherein polyglycerol polyricinoleate is present in an amount of about 0.14% wt when the fuel additive is added to biodiesel fuel present in an amount of about 99.53% wt.
 6. The fuel additive according to claim 1, wherein polyglycerol polyricinoleate is present in the additive an amount of about 10% wt.
 7. The fuel additive according to claim 1, wherein polyglycerol polyricinoleate is present in an amount of about 0.19% wt when the fuel additive is added to biodiesel fuel present in an amount of about 99.37% wt.
 8. The fuel additive according to claim 1, wherein polyglycerol polyricinoleate is present in an amount of about 0.85% wt when the fuel additive is added to biodiesel fuel present in an amount of about 98.03% wt.
 9. The fuel additive according to claim 1, wherein polyglycerol polyricinoleate is present in an amount of about 0.63% wt when the fuel additive is added to biodiesel fuel present in an amount of about 98.95% wt.
 10. The fuel additive according to claim 1, wherein the fuel additive further comprises at least one solvent.
 11. The fuel additive according to claim 1, wherein the fuel additive further comprises at least one of ethylene vinyl acetate and polyethylene vinyl acetate.
 12. The fuel additive according to claim 11, wherein the at least one of ethylene vinyl acetate and polyethylene vinyl acetate comprises ethylene vinyl acetate.
 13. The fuel additive according to claim 11, wherein the at least one of ethylene vinyl acetate and polyethylene vinyl acetate is present in an amount of about 0.13% wt when the fuel additive is added to fuel present in an amount of about 99.53% wt.
 14. The fuel additive according to claim 1, wherein the fuel additive further comprises at least one polyglycerol ester of mixed fatty acids.
 15. The fuel additive according to claim 14, wherein the at least one polyglycerol ester of mixed fatty acids is present in an amount of about 0.11% wt when the diesel fuel additive is added to fuel present in an amount of about 99.53% wt. 